Gamma Relaxation Research Articles

Gamma relaxation in Dy-based metallic glasses and its correlation with plasticity

The discovery of secondary relaxation in metallic glass (MG) breaks the longstanding cognition that MG, as a simple glassy system, exhibits only α relaxation and contributes significantly to the understanding of the structure and mechanical properties of MG. In this work, two independent fast secondary relaxation peaks corresponding to γ and β′ relaxation were detected by dynamic mechanical measurement in several Dy-based MGs at temperatures far below the glass transition temperature. Compared with β′ relaxation, the novel γ relaxation is activated at lower temperatures and possesses smaller activation energy approximately 2/3 of that for β′ relaxation. By exciting γ relaxation, loosely packed regions evolve into vein-like patterns in the fracture surface, leading to unusual plasticity at cryogenic temperatures. Furthermore, a holistic relaxation spectrum including boson peak, fast γ and β′ relaxation, slow β relaxation and primary α relaxation in MG was depicted.

The nature of the gamma dielectric relaxation in diglycidyl ether Bisphenol-A (DGEBA) based epoxies

A γ relaxation dielectric loss peak has been measured in the temperature range 113–163 K for a series of epoxy resins based on diglycidyl ether bisphenol-A (DGEBA). The network architecture of the examined systems were systematically altered using varied types of functional network modifiers featuring different functional groups. Analysis of the temperature dependence of the loss peak frequency leads to a radically new interpretation of the fundamental processes that are associated with the γ relaxation. The analysis has shown that the relaxation process can best be described in terms of a thermally assisted tunnelling displacement of a proton, termed activated tunnelling. The parameters derived not only fit the experimental data well, but have a clear physical origin that is shown to be consistent with the network topology as expressed through the glass transition temperature. The maximum temperature for which such behavior is observable has been determined and shown to be consistent with the measurements. The approach proposed here provides a new method for understanding γ relaxations in these and similar systems. Temperature T , dependence of the gamma relaxation frequency f p , for four related epoxy resin formulations. The curvature in the four data sets (◯ △ ▽ &square) is well reproduced by the activated tunnelling best fits (solid, long dash, short dash, dash dot lines), demonstrating that activated tunnelling is a better description than the traditional Arrhenius theory. • New physical understanding Gamma relaxations. • Thermally assisted proton tunnelling at local sites describes Gamma relaxation. • Activated tunnelling is a better description than the traditional Arrhenius theory. • Tunnelling parameters yield a description of the relaxation site potential surface. • Tunnelling parameters can be correlated with material topological constraints.

Thermal dielectroscopy study on the vertical and horizontal interactions in erythrocyte sub-membrane skeleton

Thermal dielectroscopy was used to study the spectrin-based sub-membrane skeleton (MS) and its attachment to the lipid bilayer of human erythrocyte membrane. At the spectrin denaturation temperature, TA, the complex impedance, Z*, and capacitance, C*, sustain sigmoid, frequency-dependent changes, ΔZ* = ΔZ' + jΔZ" and ΔC* = ΔC' - jΔC", respectively. The impedance change plot, -ΔZ" vs. ΔZ′, depicts two semicircles revealing two dielectric relaxations on MS, here designated as beta and gamma relaxations on MS [Ivanov and Paarvanova, 2016]. We report here that ortho-vanadate (5 mM), alkaline cytosole (pH 9.2), N-ethylmaleimide (5 mM), diamide (1 mM) and cell shrinkage, all known to disrupt the band 3 tetramer-spectrin attachment site, inhibited gamma relaxation, which represents the direct interaction of high frequency field with spectrin. By contrast DNAase I, diphosphoglycerate (10 mM) and urea (1–2 M), all known to disrupt the actin-spectrin junction, inhibited beta relaxation, which represents the piezo effect on spectrin, powered by the low frequency electrostriction of lipid bilayer. The frequency curves of ΔCd" (dielectric component of ΔC") and of ΔC′ both determined the critical frequencies of beta and gamma relaxations as 1.4 and 6 MHz at 46 °C (1.1 and 4.5 MHz at 37 °C), respectively. Based on the presented results, the effect of MS attachment on the dynamics and elasticity of MS was discussed.

Gamma relaxation in bulk metallic glasses

Studying the primary α- and secondary β-relaxation process has contributed significantly to the understanding of the structure and rheology of metallic glasses. In this letter, we report on a third relaxation mechanism indicated by a maximum in the loss modulus at low temperatures, which we term γ-relaxation. Contrary to the α- and β-relaxation mechanisms, this irreversible, low energy excitation causes a macroscopic rejuvenation, which we assign to non-affine atomic rearrangements in the matrix that are driven by thermal stresses during cooling. Observed in three different glassy alloys, the low temperature relaxation is identified as a general process in metallic glasses.

Molecular mobility in the supercooled and glassy states of nizatidine and perphenazine

The dielectric properties of two pharmaceuticals nizatidine and perphenazine were investigated in the supercooled liquid and glassy states by broadband dielectric spectroscopy. Two relaxation processes were observed in both the pharmaceuticals. The relaxation process observed above the glass transition temperature is the structural alpha relaxation and below the glass transition temperature is the gamma relaxation of intramolecular origin. The Johari-Goldstein beta relaxation coming from the motion of the entire molecule is found to be hidden under the structural relaxation peak in both the pharmaceuticals.

Mixture of cholesterol end-capped polyethylene glycol with DSPC liposomal

The dynamic of network of self-assembled liposome by end-capped polymer was investigated using dynamic light scattering. The liposome network, physically cross-linked by mixed liposome solutions with three different length scale of cholesterol end-capped polyethylene glycol. The network of liposome is dependent on both the polymer concentration and length scale. In the pure liposome, one motion at low time scale is observed by DLS. In the higher concentration of polymer in liposome, several motion is observed that the fast motion is alpha relaxation and other two slow motion are beta and gamma relaxations. The distance between diffusion coefficient of fast and slow relaxation is increased with increase of length scale of endcapped polymers. The SAXS data is fitted with a Percus-Yevick hard sphere model and it shows that the size of liposome increasing with increase of polymer length scale in the mixture system.

Relaxations of light scattering in mixture of PEG-PDMS-PEG triblock polymer with water in oil nano-droplets

The effect of a triblock oil soluble polymer (PEG-PDMS-PEG) on the properties of water-in-oil (W/O) droplet microemulsion (R ∼ 7.5 nm) has been studied as a function of the amount of added polymer. Macroscopically one observes a substantial increase of viscosity with increase of polymer concentration that it is surpassed and effective cross-linking of the droplets takes place. SAXS measurements show that the size of the droplets is not changed by the polymer addition but it induces repulsive interactions ones at high polymer content. One fast (alpha relaxation) and two slow relaxations (beta and gamma relaxations) were observed in mixture system by Quasielastic light scattering (QLS). At high polymer content the network formation leads to slowdown of beta and gamma relaxations in QLS and increase in the motion of alpha. Moreover, the increasing of midblock length of polymer in mixture systems can increasing the different between slow and fast relaxation.

Temperature and frequency analysis of the dynamical visco–elastic properties of high–density polyethylene

The behaviour of the dynamical visco–elastic functions in high–density polyethylene (HDPE), which carries the trade mark 'Bulen', in the region of gamma and beta relaxation transitions was studied. The method of forced torsion vibrations was used to obtain curves for the storage modulus (G′), loss modulus (G2) and loss tangent (tg δ) in the temperature interval (–180 to +20)°C and torsion frequency (0.1 to 100) rad/s. The maximum values of the storage modulus, the temperature at which these maximums appear and the full width at half maximum show an increase with the increase in the torsion frequency, but the most outstanding and prominent change is in the interval (0.1 to 10) rad/s. This fact is explained with reference to the processes of the deformational orientation of the macromolecular chain segments leading to changes in the intensity of the anelastic intermolecular interactions, the frequency response of the kinetic elements responsible for the realization of the gamma relaxation transitions, etc. The analogical frequency dependencies, derived from the loss tangent curves, show that the greatest changes take place in the same frequency interval (0.1 to 10) rad/s, although certain differences can be seen, and some of them are explained by the greater sensibility of tg δ changes in the physical kinetics of the gamma transition. The specific region in PE characterizing the local minimum of the mechanical losses is also discussed.

Thermal and dynamic mechanical properties of vitamin E infused and blended ultra‐high molecular weight polyethylenes

AbstractVitamin E (or α‐tocopherol) is an alternative via to thermal treatments to achieve oxidative stability of gamma or electron beam irradiated ultra‐high molecular weight polyethylenes (UHMWPE) used in total joint replacements. Our aim was to study the effects of vitamin E on the molecular dynamics and microstructural properties of UHMWPE. We hypothesized that the antioxidant would plasticize UHMWPE. Vitamin E was incorporated into UHMWPE at different concentrations by diffusion and blending and detected by ultraviolet and infrared spectroscopies from 500 ppm and 4000 ppm, respectively. Dynamic mechanical thermal analysis was used to characterize the influence of this antioxidant in the relaxations of the raw material. Differential scanning calorimetry and transmission electron microscopy served to characterize thermal and microstructure properties, respectively. Vitamin E concentrations above 3% by weight significantly reduced the degree of crystallinity and increased the melting transition temperature of raw UHMWPE. The presence of increasing concentrations of α‐tocopherol introduced and/or strengthened the beta relaxation, which was also shifted toward gradually lower temperatures and had rising activation energies up to 188 kJ/mol. In addition, the gamma relaxation remained unaltered on vitamin E addition. Therefore, no plasticizing effects of vitamin E on the molecular dynamics of UHMWPE could be confirmed from mechanical spectroscopy data. However, the α relaxation was modified in intensity and location due to the changes in the degree of crystallinity introduced by the incorporation of vitamin E. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Microstructural parameters controlling gas permeability and permselectivity in polyimide membranes

The present paper deals with the relationships between the gas permeation properties and the microstructural parameters of amorphous polyimides. The correlation is deduced from a data compilation of about 100 polyimides, taken from the literature or synthesized and characterized in our laboratory. The microstructure of polyimides is described on different scales through density measurement, wide-angle X-ray scattering (WAXS), UV–visible spectrophotometry, dynamic mechanical thermal analysis (DMTA) and positronium annihilation lifetime spectroscopy (PALS). From these experiments, there are only three extracted probes which display strong relationships with gas transport properties. These probes are the temperature of the gamma relaxation (Tγ), the color index ( λ 50) and the radius ( R) of the spherical free volume hole. The empirical models are based on the gas molecular diameter and on four constants for each microstructural probe. The prediction is achieved for the gas permeability coefficients of seven gas molecules and also for diffusion and sorption coefficients in some cases. The proposed fits are also consistent with the dependence of the permselectivity on the microstructural probe and gas molecule diameter.

Influence of Gamma Irradiation on Carbon Nanotube-Reinforced Polypropylene

Single walled carbon nanotubes (SWNT) have been incorporated into a polypropylene (PP) matrix in different concentrations (range: 0.25-2.5 wt%). The nanotubes were blended with PP particles (approximately 500 microm in size) before mixing in an extruder. Finally, rectangular plates were obtained by compression moulding. PP-SWNT composites were gamma irradiated at different doses, 10 and 20 kGy, to promote crosslinking in the matrix and potentially enhance the interaction between nanotubes and PP. Extensive thermal, structural and mechanical characterization was conducted by means of DSC, X-ray diffraction, Raman spectroscopy, uniaxial tensile tests and dynamic mechanical thermal (DMTA) techniques. DSC thermograms reflected higher crystallinity with increasing nanotube concentration. XRD analysis confirmed the only presence of a monoclinic crystals and proved unambiguously that CNTs generated a preferred orientation. Raman spectroscopy confirmed that the intercalation of the polymer between bundles is favored at low CNTs contents. Elastic modulus results confirmed the reinforcement of the polypropylene matrix with increasing SWNT concentration, although stiffness saturation was observed at the highest concentration. Loss tangent DMTA curves showed three transitions for raw polypropylene. While gamma relaxation remained practically unchanged in all the samples, beta relaxation temperatures showed an increase with increasing CNT content due to the reduced mobility of the system. Gamma-irradiated PP exhibited an increase in the beta relaxation temperature, associated with changes in glass transition due to radiation-induced crosslinking. On the contrary, gamma-irradiated nanocomposites did not show this effect probably due to the reaction of radiative free radicals with CNTs.

Effect of photooxidative ageing at natural conditions on dynamic mechanical properties of PE-LD/PE-LLD blends

The blends of low density polyethylene with linear low density polyethylene and pure polyolefins were blown for their use in agriculture. These films were stabilized with a commercial Hindered Amine Light Stabilized (HALS). Blends with this stabilizer were photodegraded under natural outdoor weathering conditions during two years. Photodegradation involves oxidation of the polymer chain and causes modifications of the mechanical properties of the exposed films that were monitored by dynamic mechanical spectroscopy. The mechanical relaxation spectra show the alfa, beta and gamma relaxation zones, in decreasing order of temperature. Their characterization was carried out using the deconvolution method proposed by Charlesworth, together with the Fuoss-Kirkwood equation. The results obtained for pure PE-LLD and PE-LD and their blends show that the storage modulus increases as a function of the exposure time. The maximum storage modulus is reached at different exposure times depending on the blend composition. The beta relaxation zone is the most affected by weathering. A new relaxation was detected between -85° and -75°, which was modified as a function of the exposure time, and finally even disappeared. All the samples exhibit the same evolution, but at different time scales. It has been found that after two years of exposure, the degradation of the interfacial region is already initiated. The blends with 50% of PE-LD are the most resistant to weathering.

Effect of stretching on the sub-Tgphenylene-ring dynamics of polycarbonate by neutron scattering

We have investigated the effect of cold drawing on the motion of phenylene rings in bisphenol-A polycarbonate by neutron scattering. The intensity scattered by isotropic and stretched polycarbonate is different, the quasielastic broadening being larger for the isotropic sample. This difference can be well accounted for by considering that preferentially oriented rings in the stretched polymer have their motion sterically hindered. The extent of the effect of stretching on the phenylene-ring motion obtained from this neutron-scattering investigation is in good agreement with that obtained when studying the effect of cold drawing on the gamma relaxation by dielectric spectroscopy.

Influence of structural chemical characteristics on polymer chain dynamics

A comparative study of the dielectric relaxation behavior of two structurally close polymers containing aliphatic-aromatic side groups was carried out in order to get a better understanding on how slight differences in chemical structure affect the molecular responses to perturbation fields. Specifically, chain dynamics of poly(2-acryloyloxyethyl-2-naphthalene-2-ylacetate) and poly(2-methacryloyloxyethyl-2-naphthalene-2-ylacetate) were studied by broadband dielectric spectroscopy in the frequency range of 10(-2)-10(8) Hz and temperature window of 298-403 K. Also, the relaxation behavior of (2-acetyloxyethyl-2-naphthalene-2-ylacetate), model compound of the polymer side groups, was analyzed. The isotherms representing the dielectric loss in the frequency domain show important conductive contributions, especially at high temperature, which hide the low frequency side of the alpha relaxation. Conductivity also increases the real component of the complex permittivity in the low frequencies region. Retardation spectra were obtained by minimizing the sum of the squares of the difference between the experimental values of the complex permittivity for each frequency and the analytical ones, predicted by the linear phenomenological theory, using a Tikhonov regularization technique. The spectra present an apparent alpha peak with an excess wing at short time side resulting from the overlapping of the true alpha relaxation and a beta process. Three absorptions, named in increasing order of time gamma, beta, and alpha relaxations, are separated by deconvolution methods. The activation energies associated with the gamma process are 70.0+/-1.8, 68.0+/-1.4, and 74.8+/-0.8 kJ mol(-1) for (2-acetyloxyethyl-2-naphthalene-2-yl acetate), poly(2-acryloyloxyethyl-2-naphthalene-2-yl acetate) and poly(2-methacryloyloxyethyl-2-naphthalene-2-yl acetate), respectively. The respective activation energies associated with the beta relaxation are 121.7+/-2.4, 135.3+/-1.4, and 141.6+/-1.3 kJ mol(-1). Values of the shape parameters and the strengths of the relaxation processes were obtained as a function of temperature. The dynamic fragility of the polymers and the model compound was studied and compared with that reported for macromolecular and monomeric systems. Also, the evolution of the size of the correlated domains associated with the alpha relaxation was estimated. Finally, the gamma relaxation rather than the beta absorption obeys the criteria apparently held by the Johari-Goldstein beta processes.

Dielectric Properties of PMMA/Soot Nanocomposites

Dielectric analysis (DEA) of relaxation behavior in poly(methyl methacrylate) (PMMA) soot nanocomposites is described herein. The soot, an inexpensive material, consists of carbon nanotubes, amorphous and graphitic carbon and metal particles. Results are compared to earlier studies on PMMA/multi-walled nanotube (MWNT) composites and PMMA/single-walled nanotube (SWNT) composites. The beta relaxation process appeared to be unaffected by the presence of the soot, as was noted earlier in nanotube composites. The gamma relaxation region in PMMA, normally dielectrically inactive, was "awakened" in the PMMA/soot composite. This occurrence is consistent with previously published data on nanotube composites. The dielectric permittivity, s', increased with soot content. The sample with 1% soot exhibited a permittivity (at 100 Hz and 25 degrees C) of 7.3 as compared to 5.1 for neat PMMA. Soot increased the dielectric strength, deltaE, of the composites. The 1% soot sample exhibited a dielectric strength of 6.38, while the neat PMMA had a value of 2.95 at 40 degrees C. The symmetric broadening term (alpha) was slightly higher for the 1% composite at temperatures near the secondary relaxation and near the primary relaxation, but all samples deviated from symmetrical semi-circular behavior (alpha = 1). The impact of the soot filler is seen more clearly in dielectric properties than in mechanical properties studies conducted earlier.

Phenylene ring dynamics in phenoxy and the effect of intramolecular linkages on the dynamics of some engineering thermoplastics below the glass transition temperature

We have investigated the dynamics of phenylene rings in the engineering thermoplastic bisphenol-A poly(hydroxyether) -- phenoxy -- below its glass transition temperature by means of neutron scattering techniques. A relatively wide dynamic range has been covered thanks to the combination of two different types of neutron spectrometers, time of flight and backscattering. Partially deuterated samples have been used in order to isolate the phenylene ring dynamics. The resulting neutron scattering signal of phenoxy has been described by a model that considers pi flips and oscillation motions for phenylene rings. The associated time scales are broadly distributed with mean activation energies equal to 0.41 and 0.21eV , respectively. Finally, a comparative study with the literature shows that the dielectric and mechanical gamma relaxation in phenoxy exhibit good correlation with the characteristic times of the aliphatic chain published elsewhere and with the characteristic times observed for the motion of phenylene rings by neutron scattering. These findings are discussed in a more general framework that considers, in addition, previous results on other polymers, which also contain the bisphenol-A unit.

Effect of γ-irradiation on the structure of poly(ethyl acrylate-co-hydroxyethyl methacrylate) copolymer networks for biomedical applications

The effect of the sterilization process by gamma-irradiation on the structure of poly(ethyl acrylate-co-hydroxyethyl methacrylate) copolymer networks, P(EA-co-HEMA) is studied for a broad dose range (7, 15, 25 and 50 kGy) and copolymer composition interval (0, 0.3, 0.5, 0.7 and 1 weight fraction of HEMA in the copolymer). gamma-irradiation promotes chain scission in PHEMA homopolymer but induces new crosslinking points in PEA homopolymer. Both effects are present in the copolymers, with a net result that depends on composition. For copolymers with high HEMA fractions chain scission predominates, while, as the amount of EA in the copolymer increases, the situation changes and the net effect turns out to be an increase in the number of elastically active chains. Further, gamma-irradiation strengthens the gamma relaxation in PHEMA homopolymer, what suggest that the number of interchain hydrogen bonds decreases. FTIR spectroscopy reveals no oxidation as a consequence of the sterilization process.

Dielectric secondary relaxations in polypropylene glycols

Broadband dielectric measurements of polypropylene glycol of molecular weight M(w)=400 g / mol (PPG 400) were carried out at ambient pressure over the wide temperature range from 123 to 353 K. Three relaxation processes were observed. Besides the structural alpha relaxation, two secondary relaxations, beta and gamma, were found. The beta process was identified as the true Johari-Goldstein relaxation by using a criterion based on the coupling model prediction. The faster gamma relaxation, well separated from the primary process, undoubtedly exhibits the anomalous behavior near the glass transition temperature (T(g)) which is reflected in the presence of a minimum of the temperature dependence of the gamma-relaxation time. We successfully applied the minimal model [Dyre and Olsen, Phys. Rev. Lett. 91, 155703 (2003)] to describe the entire temperature dependence of the gamma-relaxation time. The asymmetric double-well potential parameters obtained by Dyre and Olsen for the secondary relaxation of tripropylene glycol at ambient pressure were modified by fitting to the minimal model at lower temperatures. Moreover, we showed that the effect of the molecular weight of polypropylene glycol on the minimal model parameters is significantly larger than that of the high pressure. Such results can be explained by the smaller degree of hydrogen bonds formed by longer chain molecules of PPG at ambient pressure than that created by shorter chains of PPG at high pressure.

Primary and secondary relaxations in supercooled eugenol and isoeugenol at ambient and elevated pressures: Dependence on chemical microstructure

Dielectric loss spectra of two glass-forming isomers, eugenol and isoeugenol, measured at ambient and elevated pressures in the normal liquid, supercooled, and glassy states are presented. The isomeric chemical compounds studied differ only by the location of the double bond in the alkyl chain. Above the glass transition temperature T(g), the dielectric loss spectra of both isomers exhibit an excess wing on the high frequency flank of the loss peak of the alpha relaxation and an additional faster gamma process at the megahertz frequency range. By decreasing temperature below T(g) at ambient pressure or by elevating pressure above P(g), the glass transition pressure, at constant temperature, the excess wing of isoeugenol shifts to lower frequencies and is transformed into a secondary beta-loss peak, while in eugenol it becomes a shoulder. These spectral features enable the beta-relaxation time tau(beta) to be determined in the glassy state. These changes indicate that the excess wings in isoeugenol and eugenol are similar and both are secondary beta relaxations that are not resolved in the liquid state. While in both isoeugenol and eugenol the loss peak of the beta relaxation in the glassy state and the corresponding excess wing in the liquid state shifts to lower frequencies on elevating pressure, the locations of their gamma relaxation show little change with increasing pressure. The different pressure sensitivities of the excess wing and gamma relaxation are further demonstrated by the nearly perfect superposition of the alpha-loss peak together with excess wing from the data taken at ambient pressure and at elevated pressure (and higher temperature so as to have the same alpha-peak frequency), but not the gamma-loss peak in both isoeugenol and eugenol. On physical aging isoeugenol, the beta-loss peak shifts to lower frequencies, but not the gamma relaxation. Basing on these experimental facts, the faster gamma relaxation is a local intramolecular process involving a side group and the slower beta relaxation mimics the structural alpha relaxation in behavior, involves the entire molecule and satisfies the criteria for being the Johari-Goldstein beta relaxation. Analysis and interpretation of the spectra utilizing the coupling model further demonstrate that the excess wings seen in the equilibrium liquid states of these two isomers are their genuine Johari-Goldstein beta relaxation.

Sub-Tg dynamics in polycarbonate by neutron scattering and its relation with secondary γ relaxation

We have investigated the dynamics of phenylene rings in glassy bisphenol-A (BPA) polycarbonate (PC) by means of quasielastic neutron scattering. Taking advantage of selective deuteration of the samples, we have studied the incoherent scattering of hydrogens in phenylene rings on the one hand, and on the other hand the coherent quasielastic scattering of all the atoms in the sample. Two different types of neutron spectrometers, time of flight and backscattering, were used in order to cover a wide dynamic range, which extends from microscopic (approximately 10(-13) s) to mesoscopic (approximately 10(-9) s) times. Moreover, neutron-diffraction experiments with polarization analysis were carried out in order to characterize the structural features, and the relative coherent and incoherent contributions of the samples investigated. In contrast with previous studies of phenylene ring dynamics in BPA polysulfone performed by us also by neutron scattering, phenylene rings in BPA PC exhibit an "extra" motion in addition to those found for BPA polysulfone's phenylene rings. This extra motion of the rings in PC perfectly correlates with the main carbonate group motion followed by dielectric spectroscopy and allows us to (i) consistently interpret the PC's gamma relaxation in terms of two different motions; and (ii) experimentally confirm the relation between the motion of phenylene rings and carbonate groups within BPA PC formerly predicted by computational methods.